CN114774704B - Method for producing low-lead tin-based Babbitt alloy by utilizing tin refining slag - Google Patents
Method for producing low-lead tin-based Babbitt alloy by utilizing tin refining slag Download PDFInfo
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- CN114774704B CN114774704B CN202210420546.7A CN202210420546A CN114774704B CN 114774704 B CN114774704 B CN 114774704B CN 202210420546 A CN202210420546 A CN 202210420546A CN 114774704 B CN114774704 B CN 114774704B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
Abstract
A method for producing low-lead tin-based babbitt alloy by using tin refining slag, which comprises the following steps: (1) Adding the copper-sulfur slag removed by crude tin refining, arsenic-antimony-aluminum slag removed by crude tin refining, tin calcine, limestone and river sand into a reduction smelting furnace according to a certain material proportion; (2) Carrying out centrifugal iron removal and deep iron removal on the produced crude tin with high copper content and high antimony content; (3) Feeding high copper and antimony crude tin with iron content less than or equal to 0.01% into a high-temperature vacuum distillation separation furnace for removing arsenic, lead and bismuth to produce high copper and antimony crude tin alloy; (4) And (3) respectively adding copper, antimony and other elements into the high-copper antimony crude tin alloy according to the requirement of tin-based Babbitt alloy elements to produce a low-lead tin-based Babbitt alloy product. The method has the advantages of simple process operation condition, high mechanical automation degree, short flow, environment-friendly production process, less production amount of smelting waste slag, no production of arsenic aluminum slag which is a highly toxic substance and high tin smelting recovery rate.
Description
Technical Field
The invention relates to the field of comprehensive recovery of valuable metals of crude tin refining slag and new materials, in particular to a method for producing low-lead tin-based Babbitt alloy by utilizing tin refining slag.
Background
Tin-based Babbitt metal is an alloy which is prepared by adding elements such as antimony and copper based on tin, is also called tin-based bearing alloy or tin-based white alloy, and is a bearing material widely applied in industry. Common tin-based Babbitt alloys include Sn-12Sb-4Cu-10Pb, sn-11Sb-6Cu, sn-8Sb-4Cu, sn-4Sb-4Cu, etc., and among these, the low-lead tin-based Babbitt alloys have the most wide application and use amount. The existing method for producing the tin-based Babbitt alloy mainly comprises the steps of preparing pure metal ingots of tin, antimony and copper and recycling the conventional smelting process of tin smelting slag, and the disadvantage of preparing the tin-based Babbitt alloy from the pure metal ingots of tin, antimony and copper is that the produced Babbitt alloy product has no market competitiveness and low market bidding and bargaining capacity; the conventional smelting process recycling of tin smelting slag generally has a certain process configuration in large-scale tin smelting enterprises, the main method is to perform reduction smelting on tin refining slag and tin concentrate in a reducing furnace to produce high-antimony copper crude tin, and then perform iron removal, arsenic removal, lead removal and bismuth removal according to the conventional tin refining process, such as aluminum addition and arsenic removal, and partial removal of element antimony is caused at the same time of arsenic removal due to the similar chemical characteristics of arsenic and antimony, and extremely toxic substances aluminum-arsenic-antimony slag (arsenic-arsenic slag produced when water is met or arsenic hydride toxic gas is produced when moisture is met) is also produced; for example, lead and bismuth are removed by a crystallizer, the lead and bismuth removing capability of the crystallizer is low, the energy consumption is high, the operation difficulty of the crystallizer is high, the failure rate is high and the like due to high content of multi-element metals such as copper and antimony in crude tin, and meanwhile, the direct yield of tin smelting is reduced and valuable metal slag is lost due to the fact that a large amount of tin refining slag is produced due to overlong process flow.
Disclosure of Invention
Aiming at the problems, the invention provides a method for producing low-lead tin-based Babbitt alloy by using tin refining slag, which has the advantages of simple process operation condition, high mechanical automation degree, short flow, environment-friendly production process, less production amount of smelting slag, no generation of arsenic-aluminum slag which is a highly toxic substance, high tin smelting recovery rate, and high comprehensive recovery and utilization rate of valuable metals, which is far higher than that of the conventional low-lead tin-based Babbitt alloy production process, and can effectively improve the value of the valuable metal elements in tin concentrate and improve the comprehensive recovery of resources and market bidding bargaining capability of tin smelting enterprises.
In order to achieve the above object, the technical scheme of the present invention is as follows: a method for producing low-lead tin-based babbitt alloy by using tin refining slag, which comprises the following steps:
(1) The copper-sulfur-removing slag, arsenic-antimony-removing aluminum slag, tin calcine, limestone and river sand during crude tin refining are put into a reduction smelting furnace according to a certain material proportion;
(2) Performing condensation and centrifugal deironing on the produced crude tin with high copper content and antimony content, and deeply deironing by using a condensation deironing agent to remove the crude tin iron to below 0.08%;
(3) Feeding high copper and antimony crude tin with iron content less than or equal to 0.08% into a high-temperature vacuum distillation separation furnace to remove arsenic, lead and bismuth, and obtaining high copper and antimony crude tin alloy with As content less than or equal to 0.05%, pb content less than or equal to 0.01% and Bi content less than or equal to 0.08%;
(4) The high copper-antimony crude tin alloy containing As less than or equal to 0.01%, pb less than or equal to 0.35% and Bi less than or equal to 0.01% is respectively mixed with copper and antimony elements according to the requirement of low lead-tin base Babbitt alloy elements, and the low lead-tin base Babbitt alloy product is produced.
The copper-sulfur-removing slag and the arsenic-antimony-removing aluminum slag produced in the step (1) during the crude tin refining are copper-sulfur-removing slag produced by adding sulfur and copper for copper removal in the crude tin refining, and arsenic-antimony-removing aluminum slag produced by adding aluminum for arsenic and antimony removal in the crude tin refining.
The low-lead tin-based Babbitt alloy is a tin-based Babbitt alloy containing less than 0.35% lead;
the materials of the step (1) of removing arsenic and antimony aluminum slag, removing copper and sulfur slag, tin calcine, limestone and river sand are proportioned according to the proportion of 1-1.5 of the acidity of high-temperature reduction furnace smelting slag, the produced crude tin contains 3-8% of copper and 4-8% of antimony, and the reduction smelting temperature is 1100-1300 ℃.
The temperature range of the condensate deironing and the deep deironing is 250-400 ℃, the deironing agent is wood dust and ammonium chloride, and the condensate cooling adopts a water cooling mode;
and (3) feeding the high copper and antimony crude tin with iron content less than or equal to 0.08% into a high-temperature vacuum distillation separation furnace at the feeding temperature of 350-500 ℃, the operating temperature of the vacuum distillation separation furnace of 950-1200 ℃, the distillation time of 5-30mins and the vacuum degree of 10-50Pa.
And (4) according to different low-lead Babbitt alloy components, combining high-copper antimony crude tin alloy components containing As less than or equal to 0.01%, pb less than or equal to 0.35% and Bi less than or equal to 0.01%, and adding different metals to prepare the low-lead tin-based Babbitt alloy product.
The percentages stated in the invention are mass percentages except for the other description, and the sum of the percentages of the components is 100%.
The invention has the advantages that:
(1) Short flow, simple process operation condition and high mechanical automation degree;
(2) The production process is environment-friendly, the production amount of smelting waste slag is small, and no highly toxic substance arsenic aluminum slag is produced;
(3) The recovery rate of smelting the Babbitt metal produced by using the tin refining slag is high;
(4) The comprehensive recovery rate of the Babbitt metal copper and the antimony valuable metals produced by using the tin refining slag is high, and the utilization rate of the copper and the antimony valuable metals is high.
Detailed Description
The technical scheme of the invention is further described in detail by examples.
Example 1
This example is an example of the method for producing low-lead tin-based babbitt alloy using tin refining slag according to the present invention, comprising the steps of:
(1) Roasting tin: tin copper and sulfur removal slag: arsenic and antimony removing aluminum slag is prepared by the following steps of: 10: proportioning according to a proportion of 20, and mixing limestone and river sand to control the acidity of the reduction smelting silicon to be 1.2, and controlling the reduction temperature to be 1150 ℃ to produce crude tin containing 9.2% of copper and 8.4% of antimony;
(2) Controlling the condensing iron removal temperature to 280 ℃, adding wood dust and ammonium chloride for multiple times to deeply remove iron, and removing iron in the crude tin to 0.05%;
(3) Heating crude tin with iron content less than 0.05% to 450 ℃, feeding the crude tin into a vacuum distillation furnace to separate lead, bismuth and arsenic, controlling the temperature to 1200 ℃, controlling the vacuum degree to 40Pa, and distilling and separating for 5min to obtain high copper-antimony crude tin alloy containing As less than or equal to 0.05%, pb less than or equal to 0.01%, bi less than or equal to 0.08%, cu10% and Sb 9%;
(4) According to the chemical composition requirements of Babbitt alloy, the 1t high copper antimony crude tin alloy is respectively mixed with 0.12t antimony ingot and 0.7t tin ingot to produce Babbitt alloy containing 11% of Sb and 6% of Cu.
Example 2
This example is another example of the method for producing low lead tin-based babbitt alloy using tin refining slag according to the present invention, comprising the steps of:
(1) Roasting tin: tin copper and sulfur removal slag: arsenic and antimony removing aluminum slag is prepared by the following steps: 9:15, mixing, and adding limestone and river sand to control the acidity of the reduction smelting silicon to be 1.3, and controlling the reduction temperature to 1150 ℃ to produce crude tin containing 7% copper and 10% antimony;
(2) Controlling the condensing iron removal temperature to 280 ℃, adding wood dust and ammonium chloride for multiple times to deeply remove iron, and removing iron in the crude tin to 0.05%;
(3) Heating crude tin with iron content less than 0.05% to 450 ℃, feeding the crude tin into a vacuum distillation furnace to separate lead, bismuth and arsenic, controlling the temperature to 1200 ℃, controlling the vacuum degree to 40Pa, and distilling and separating for 5min to obtain high copper-antimony crude tin alloy containing As less than or equal to 0.05%, pb less than or equal to 0.01%, bi less than or equal to 0.08%, cu9.5% and Sb 13%;
(4) According to the chemical composition requirements of Babbitt alloy, the 1t high copper antimony crude tin alloy is respectively added with 0.07t antimony ingot and 0.65t tin ingot to produce Babbitt alloy containing 11% of Sb and 6% of Cu
Example 3
This example is a further example of the method of producing a low lead tin base babbitt alloy using tin refining slag according to the present invention, comprising the steps of:
(1) Roasting tin: tin copper and sulfur removal slag: arsenic and antimony removing aluminum slag is prepared by the following steps: 10:8, proportioning, and mixing limestone and river sand to control the acidity of the reduction smelting silicon to 1.5, and controlling the reduction temperature to 1250 ℃ to produce crude tin containing 9% of copper and 5% of antimony;
(2) Controlling the condensing iron removal temperature to 280 ℃, adding wood dust and ammonium chloride for multiple times to deeply remove iron, and removing iron in the crude tin to 0.05%;
(3) Heating crude tin with iron content less than 0.05% to 450 ℃, feeding the crude tin into a vacuum distillation furnace to separate lead, bismuth and arsenic, controlling the temperature to 1200 ℃, controlling the vacuum degree to 40Pa, and distilling and separating for 5min to obtain high copper-antimony crude tin alloy containing As less than or equal to 0.05%, pb less than or equal to 0.01%, bi less than or equal to 0.08%, cu11% and Sb 7.5%;
(4) According to the chemical composition requirements of Babbitt alloy, the 1t high copper antimony crude tin alloy is respectively mixed with 0.14t antimony ingot and 0.81t tin ingot to produce Babbitt alloy containing 11% of Sb and 6% of Cu.
Claims (4)
1. A method for producing low-lead tin-based babbitt alloy by using tin refining slag, which is characterized by comprising the following steps:
(1) The copper-sulfur-removing slag and arsenic-antimony-removing aluminum slag, tin calcine, limestone and river sand during crude tin refining are put into a reduction smelting furnace according to a certain material proportion,
the material proportion of the arsenic and antimony removing aluminum slag, copper and sulfur slag, tin calcine, limestone and river sand is 1 to 1.5 percent of the silicon acidity of the smelting slag of the high-temperature reduction furnace, the produced crude tin contains 3 to 8 percent of copper and 4 to 8 percent of antimony, and the reduction smelting temperature is 1100 to 1300 ℃;
(2) Performing condensation and centrifugal deironing on the produced crude tin with high copper content and antimony content, deeply deironing by using a condensation deironing agent, removing the crude tin iron to below 0.08 percent,
the temperature range of the condensate deironing and the deep deironing is 250-400 ℃, the deironing agent is wood dust and ammonium chloride, and the condensate cooling adopts a water cooling mode;
(3) Feeding high copper and antimony crude tin with iron content less than or equal to 0.08% into a high temperature vacuum distillation separation furnace to remove arsenic, lead and bismuth to obtain high copper and antimony crude tin alloy with As content less than or equal to 0.05%, pb content less than or equal to 0.01% and Bi content less than or equal to 0.08%,
feeding the high copper and antimony crude tin with iron content less than or equal to 0.08% into a high-temperature vacuum distillation separation furnace at the feeding temperature of 350-500 ℃, the operating temperature of the vacuum distillation separation furnace of 950-1200 ℃, the distillation time of 5-30mins and the vacuum degree of 10-50Pa;
(4) The high copper-antimony crude tin alloy containing As less than or equal to 0.01%, pb less than or equal to 0.35% and Bi less than or equal to 0.01% is respectively mixed with copper and antimony elements according to the requirement of low lead-tin base Babbitt alloy elements, and the low lead-tin base Babbitt alloy product is produced.
2. The method for producing a low-lead tin-based babbitt alloy using tin refining slag as set forth in claim 1, wherein: the copper-sulfur-removing slag and the arsenic-antimony-removing aluminum slag produced in the step (1) during the crude tin refining are copper-sulfur-removing slag produced by adding sulfur and copper for copper removal in the crude tin refining, and arsenic-antimony-removing aluminum slag produced by adding aluminum for arsenic and antimony removal in the crude tin refining.
3. The method for producing a low-lead tin-based babbitt alloy using tin refining slag as set forth in claim 1, wherein: the low-lead tin-based babbitt alloy is a tin-based babbitt alloy containing less than 0.35% lead.
4. The method for producing a low-lead tin-based babbitt alloy using tin refining slag as set forth in claim 1, wherein: and (4) according to different low-lead Babbitt alloy components, combining high-copper antimony crude tin alloy components containing As less than or equal to 0.01%, pb less than or equal to 0.35% and Bi less than or equal to 0.01%, and adding different metals to prepare the low-lead tin-based Babbitt alloy product.
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